US4101465A
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US
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A cocatalyst system for trimerizing isocyanates
Assignee: Pharmacia and Upjohn Co
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Filing: 1976-10-06
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Granted: 1978-07-18
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Expires: 1996-10-06
Abstract
Abstract A novel cocatalyst combination for the trimerization of polyisocyanates to polyisocyanurates is disclosed. The catalyst combination comprises: (a) alkali metal glycine salts, (b) hydroxyalkyltrialkylammonium carboxylate salts, and (c) alkali metal salts selected from the group consisting of (i) alkali metal salts of N-phenyl aliphatic amides, and (ii) alkali metal salts of aliphatic carboxylic acids. The use of the cocatalyst combination provides for the facile formation of polyisocyanurate foam laminate boardstock which is characterized by good fire resistance and good physical properties.
Inventors
- 👤 Robert J. Lockwood
- 👤 Alexander McLaughlin
- 👤 Harold E. Reymore, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 11:10
CPC Classifications
B; B32; B32B; B32B5/00; B32B5/22; C; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/16; C08G18/161; C08G18/163; B32B5/18; C08G18/18; C08G18/1875; C08G18/22; C08G18/225; B32B2266/00; B32B2266/02; B32B2266/0214; C08G2115/00; C08G2115/02; Y; Y10; Y10S; Y10S521/00; Y10S521/902; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31547
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
265 words
In a process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent, an organic polyisocyanate, a trimerization catalyst, and a minor amount of a polyol, the improvement which comprises employing as the catalyst, a combination consisting essentially of: (a) a glycine salt having the formula ##STR13## wherein M is an alkali metal, R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms, and R 2 is selected from the class consisting of hydrogen and the group ##STR14## (b) a hydroxyalkyltrialkylammonium carboxylate salt having the formula ##STR15## wherein R 3 , R 4 , R 5 can be the same or different and represent alkyl having from 1 to 4 carbon atoms, inclusive, R 6 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms, inclusive, and R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms, inclusive; and (c) an alkali metal salt selected from the group consisting of (i) an amide salt having the formula ##STR16## wherein M is as defined hereinbefore, R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; and (ii) a carboxylic acid salt having the formula ##STR17## wherein R 8 , R 9 , R 10 and M are as defined hereinbefore.
Claim 2
Dependent Claim
265 words
In a process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent, an organic polyisocyanate, a trimerization catalyst, and a minor amount of a polyol, the improvement which comprises employing as the catalyst, a combination consisting essentially of: (a) a glycine salt having the formula ##STR13## wherein M is an alkali metal, R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms, and R 2 is selected from the class consisting of hydrogen and the group ##STR14## (b) a hydroxyalkyltrialkylammonium carboxylate salt having the formula ##STR15## wherein R 3 , R 4 , R 5 can be the same or different and represent alkyl having from 1 to 4 carbon atoms, inclusive, R 6 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms, inclusive, and R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms, inclusive; and (c) an alkali metal salt selected from the group consisting of (i) an amide salt having the formula ##STR16## wherein M is as defined hereinbefore, R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; and (ii) a carboxylic acid salt having the formula ##STR17## wherein R 8 , R 9 , R 10 and M are as defined hereinbefore.
Claim 3
Dependent Claim
15 words
A process according to claim 1 wherein the organic polyisocyanate is a polymethylene polyphenyl polyisocyanate.
Claim 4
Dependent Claim
184 words
A process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent: (A) a polymethylene polyphenylisocyanate; (B) a minor amount of a polyol; and (C) a catalyst combination consisting essentially of (a) a glycine salt having the formula ##STR18## wherein R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms; (b) a 2-hydroxypropyltrimethylammonium carboxylate salt having the formula ##STR19## wherein R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) a potassium salt selected from the group consisting of (i) an amide salt having the formula ##STR20## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; and (ii) a carboxylic acid salt having the formula ##STR21## wherein R 8 , R 9 , and R 10 are as defined above.
Claim 5
Dependent Claim
184 words
A process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent: (A) a polymethylene polyphenylisocyanate; (B) a minor amount of a polyol; and (C) a catalyst combination consisting essentially of (a) a glycine salt having the formula ##STR18## wherein R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms; (b) a 2-hydroxypropyltrimethylammonium carboxylate salt having the formula ##STR19## wherein R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) a potassium salt selected from the group consisting of (i) an amide salt having the formula ##STR20## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; and (ii) a carboxylic acid salt having the formula ##STR21## wherein R 8 , R 9 , and R 10 are as defined above.
Claim 6
Dependent Claim
41 words
A process according to claim 3 wherein the polymethylene polyphenylisocyanate is a mixture containing from about 30 percent to about 85 percent by weight of methylenebis (phenylisocyanate) and the remainder of said mixture comprises polymethylene polyphenylisocyanates of functionality higher than 2.0.
Claim 7
Dependent Claim
42 words
A process according to claim 4 wherein said polyisocyanate has been previously treated with about 0.25 equivalent to about 1.0 equivalent of a monomeric epoxide per equivalent of acid present in said polyisocyanate to reduce acidity to less than about 0.10 percent.
Claim 8
Dependent Claim
37 words
A process according to claim 3 wherein said glycine salt (a) is sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate and is present in the form of a solution from about 25 percent to about 75 percent by weight in diethylene glycol.
Claim 9
Dependent Claim
37 words
A process according to claim 3 wherein said ammonium salt (b) is 2-hydroxypropyltrimethylammonium formate and is present in the form of a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 10
Dependent Claim
37 words
A process according to claim 3 wherein said ammonium salt (b) is 2-hydroxypropyltrimethylammonium 2-ethylhexanoate and is present in the form of a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 11
Dependent Claim
47 words
A process according to claim 3 wherein said potassium salt (c) is ##STR22## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive.
Claim 12
Dependent Claim
45 words
A process according to claim 9 wherein said potassium salt is potassium N-phenyl-2-ethylhexamide and is present in the form of a solution of from about 25 percent to about 75 percent by eight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 13
Dependent Claim
47 words
A process according to claim 3 wherein said potassium salt (c) is ##STR23## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive.
Claim 14
Dependent Claim
33 words
A process according to claim 11 wherein said potassium salt is potassium acetate and is present in a solution of from about 25 percent to about 75 percent by weight in ethylene glycol.
Claim 15
Dependent Claim
33 words
A process according to claim 11 wherein said potassium salt is potassium 2-ethylhexanoate and is present in a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 16
Dependent Claim
206 words
A process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent: (A) a polymethylene polyphenylisocyanate mixture containing about 30 percent to about 40 percent by weight of methylenebis(phenylisocyanate) and the remainder of said mixture comprises polymethylene polyphenylisocyanates of functionality higher than 2.0 and wherein said polyphenylisocyanate mixture has been previously mixed at room temperature with about 0.25 equivalent to about 1.0 equivalent of a monomeric epoxide per equivalent of acid present in said polyisocyanate to reduce acidity to less than about 0.10 percent; (B) a minor amount of a polyol; and (C) a catalyst combination consisting essentially of (a) sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate wherein said glycinate is present in the form of a solution of about 50 percent by weight in diethylene glycol; (b) 2-hydroxypropyltrimethylammonium 2-ethylhexanoate wherein said hexanoate is present in the form of a solution of about 54 percent by weight in about a 2:1 mixture by weight of chloroform and dipropylene glycol; and (c) potassium N-phenyl-2-ethylhexamide wherein said hexamide is present in the form of a solution of about 45 percent by weight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 17
Dependent Claim
206 words
A process for the preparation of a cellular polymer in which the major recurring polymer unit is isocyanurate which process comprises bringing together in the presence of a blowing agent: (A) a polymethylene polyphenylisocyanate mixture containing about 30 percent to about 40 percent by weight of methylenebis(phenylisocyanate) and the remainder of said mixture comprises polymethylene polyphenylisocyanates of functionality higher than 2.0 and wherein said polyphenylisocyanate mixture has been previously mixed at room temperature with about 0.25 equivalent to about 1.0 equivalent of a monomeric epoxide per equivalent of acid present in said polyisocyanate to reduce acidity to less than about 0.10 percent; (B) a minor amount of a polyol; and (C) a catalyst combination consisting essentially of (a) sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate wherein said glycinate is present in the form of a solution of about 50 percent by weight in diethylene glycol; (b) 2-hydroxypropyltrimethylammonium 2-ethylhexanoate wherein said hexanoate is present in the form of a solution of about 54 percent by weight in about a 2:1 mixture by weight of chloroform and dipropylene glycol; and (c) potassium N-phenyl-2-ethylhexamide wherein said hexamide is present in the form of a solution of about 45 percent by weight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 18
Dependent Claim
248 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of (a) from about 11 to about 85 mole percent of a glycine salt having the formula ##STR24## wherein M is an alkali metal, R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms, and R 2 is selected from the class consisting of hydrogen and the group ##STR25## (b) from about 4 to about 63 mole percent of a hydroxyalkyltrialkylammonium carboxylate salt having the formula ##STR26## wherein R 3 , R 4 and R 5 can be the same or different and represent alkyl having from 1 to 4 carbon atoms, inclusive, R 6 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms, inclusive, and R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) from about 6 to 77 mole percent of an alkali metal salt selected from the group consisting of (i) an amide salt having the formula ##STR27## wherein M is as defined hereinbefore, R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive, and (ii) a carboxylic acid salt having the formula ##STR28## wherein R 8 , R 9 , R 10 , and M are as defined hereinbefore.
Claim 19
Dependent Claim
248 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of (a) from about 11 to about 85 mole percent of a glycine salt having the formula ##STR24## wherein M is an alkali metal, R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms, and R 2 is selected from the class consisting of hydrogen and the group ##STR25## (b) from about 4 to about 63 mole percent of a hydroxyalkyltrialkylammonium carboxylate salt having the formula ##STR26## wherein R 3 , R 4 and R 5 can be the same or different and represent alkyl having from 1 to 4 carbon atoms, inclusive, R 6 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms, inclusive, and R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) from about 6 to 77 mole percent of an alkali metal salt selected from the group consisting of (i) an amide salt having the formula ##STR27## wherein M is as defined hereinbefore, R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive, and (ii) a carboxylic acid salt having the formula ##STR28## wherein R 8 , R 9 , R 10 , and M are as defined hereinbefore.
Claim 20
Dependent Claim
173 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of: (a) from about 11 to about 85 mole percent of a glycine salt having the formula ##STR29## wherein R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms; (b) from about 4 to about 63 mole percent of a 2-hydroxypropyltrimethylammonium carboxylate salt having the formula ##STR30## wherein R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) from about 6 to about 77 mole percent of a potassium salt selected from the group consisting of (i) an amide salt having the formula ##STR31## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; (ii) a carboxylic acid salt having the formula ##STR32## wherein R 8 , R 9 and R 10 are as defined above.
Claim 21
Dependent Claim
173 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of: (a) from about 11 to about 85 mole percent of a glycine salt having the formula ##STR29## wherein R 1 is selected from the class consisting of hydrogen and alkyl having from 1 to 12 carbon atoms; (b) from about 4 to about 63 mole percent of a 2-hydroxypropyltrimethylammonium carboxylate salt having the formula ##STR30## wherein R 7 is selected from the class consisting of hydrogen and alkyl having from 1 to 8 carbon atoms inclusive; and (c) from about 6 to about 77 mole percent of a potassium salt selected from the group consisting of (i) an amide salt having the formula ##STR31## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive; (ii) a carboxylic acid salt having the formula ##STR32## wherein R 8 , R 9 and R 10 are as defined above.
Claim 22
Dependent Claim
38 words
A cocatalyst according to claim 16 wherein said glycine salt (a) is sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate and is present in the form of a solution of from about 25 percent to about 75 percent by weight in diethylene glycol.
Claim 23
Dependent Claim
37 words
A cocatalyst according to claim 16 wherein said ammmonium salt (b) is 2-hydroxypropyltrimethylammonium formate and is present in the form of a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 24
Dependent Claim
36 words
A cocatalyst according to claim 16 wherein said ammonium salt (b) is 2-hydroxypropyltrimethylammonium-2-ethylhexanoate and is present in the form of a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 25
Dependent Claim
47 words
A cocatalyst according to claim 16 wherein said potassium salt (c) is ##STR33## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atom, inclusive.
Claim 26
Dependent Claim
44 words
A cocatalyst according to claim 20 wherein said potassium salt is N-phenyl-2-ethylhexamide and is present in the form of a solution of from about 25 percent to about 75 percent by weight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 27
Dependent Claim
47 words
A cocatalyst according to claim 16 wherein said potassium salt (c) is ##STR34## wherein R 8 , R 9 , and R 10 can be the same or different and are selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms, inclusive.
Claim 28
Dependent Claim
33 words
A cocatalyst according to claim 22 wherein said potassium salt is potassium acetate and is present in a solution of from about 25 percent to about 75 percent by weight in ethylene glycol.
Claim 29
Dependent Claim
33 words
A cocatalyst according to claim 22 wherein said potassium salt is potassium 2-ethylhexanoate and is present in a solution of from about 25 percent to about 75 percent by weight in dipropylene glycol.
Claim 30
Dependent Claim
128 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of: (a) from about 35 to about 65 mole percent of sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate wherein said glycinate is present in the form of a solution of about 50 percent by weight in diethylene glycol; (b) from about 10 to about 36 mole percent of 2-hydroxypropyltrimethylammonium-2-ethylhexanoate wherein said hexanoate is present in the form of a solution of about 54 percent by weight in about a 2:1 mixture by weight of chloroform and dipropylene glycol; and (c) from about 18 to about 43 mole percent of potassium N-phenyl-2-ethylhexamide wherein said hexamide is present in the form of a solution of about 45 percent by weight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 31
Dependent Claim
128 words
A cocatalyst combination for the trimerization of an organic polyisocyanate consisting essentially of: (a) from about 35 to about 65 mole percent of sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate wherein said glycinate is present in the form of a solution of about 50 percent by weight in diethylene glycol; (b) from about 10 to about 36 mole percent of 2-hydroxypropyltrimethylammonium-2-ethylhexanoate wherein said hexanoate is present in the form of a solution of about 54 percent by weight in about a 2:1 mixture by weight of chloroform and dipropylene glycol; and (c) from about 18 to about 43 mole percent of potassium N-phenyl-2-ethylhexamide wherein said hexamide is present in the form of a solution of about 45 percent by weight in about a 1:1 mixture by weight of ethylene glycol and dimethylformamide.
Claim 32
Dependent Claim
31 words
A laminate panel comprising a foam core made in accordance with the process set forth in claim 1 and having the opposing faces of said core bonded to a facing material.
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1981-07-17 | 1982-01-16 | 1982-07-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-07-17 | 1986-01-16 | 1986-07-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-07-17 | 1990-01-16 | 1990-07-18 | $7700.00 | Window Closed / Lapsed |